Surfactant compositions for well cleaning

ABSTRACT

A surfactant composition for use in well treatment, particularly for removing oil-based mud deposits from a well prior to cementing, comprises an alkylpolyglucoside in a solution of a mutual solvent for water and hydrocarbon. The composition can be used to formulate a chemical wash by dissolving the composition at a concentration of about 1%-10% (e.g. 5%) by weight in water or brine.

[0001] The present invention relates to surfactant compositions, in particular surfactant compositions for use in cleaning oil wells or the like. The invention also comprises methods of cleaning or treating a well as part of a cementing operation.

[0002] In the drilling of a well such as an oil or gas well, a drilling fluid, often called “mud” is used to transport drilled material back to the surface and to provide support to the well and to balance the pressure of fluids in the formation through which the well is drilled. These fluids are typically suspensions of solid particulate materials including clays such as bentonite and heavy minerals such as barite in a liquid continuous phase, usually water or brine. These particulate materials provide the fluid with appropriate viscosity and thixotropic behaviour to ensure that drilled cuttings are transported to the surface and with appropriate density to balance the pressure of the formation fluids and prevent influxes. Other materials often included are fluid-loss control materials. In certain cases, fluid will tend to pass from the well into the porous and permeable rock surrounding the well due to a higher hydrostatic pressure of the fluid in the well compared to the fluids in the formation which can occur from time to time. This is often called “invasion” and is undesirable since the drilling fluid displaces the formation fluids and creates a barrier to flow of the formation fluids into the well when it is completed and allowed to produce hydrocarbons. Fluid-loss control agents are particulate materials that are allowed to build up on the wall of the well to create a solid barrier to the flow of fluid into the formation. In fact, such a layer will often form from the normal drilling fluid solids (bentonite, barite, drilled materials, etc.) and is often called “mudcake”. In many cases, gelled mud deposits can form on the walls of the well (or on top of the mudcake), or on casing or other tubulars in the well.

[0003] From time to time in the drilling of a well, it is necessary to cement a steel casing into the well to provide physical support for the well and to provide isolation between the various fluid-containing zones of the formation penetrated by the well. In order to do this, the casing is positioned in the well and cement pumped down the casing and allowed to rise up the outside and fill the annulus between the outside of the casing and the wall of the well. In order to provide effective zonal isolation, it is necessary that the cement makes a good bond with the wall and the presence of mudcake can interfere with, or completely prevent this from occurring. Therefore, it is necessary to make sure that mudcake and gelled deposits are removed from the wall before the cement is placed. Gelled fluid deposits can be removed using a “wash” fluid which is pumped through the casing and annulus and scratchers or other such tools can be used to remove mudcake if required (other fluids such as spacers are also pumped to ensure removal of drilling fluids before cementing commences).

[0004] Certain wells are drilled using oil-based drilling fluids (“oil-based muds” or “OBM”) in which a hydrocarbon is used as the continuous liquid phase other components being present in the form of an emulsion. Examples of situations where OBM might be used as when drilling through formations that swell in contact with water or are eroded quickly in contact with water. Another situation is where the well is deviated from vertical and contact between the drill string and the wall of the well is extensive and lubrication is required. The main advantages of using OBM when drilling are, better stability of the bore hole is achieved as no or little leaching of the formation occurs, better lubrication, and better cooling of the drilling bit. OBMs can provide particular problems in cementing since removal of mud deposits can be difficult. As cement slurries are usually aqueous. Removal of gelled OBM is important to ensure water-wet surfaces in the well to allow a good bond with cement. Most oil-base drilling fluids are incompatible with aqueous cement slurries. Commingling of the mud and the cement slurry can result in the build-up of an unpredictable and viscous sludge at the mud/cement interface which can cause serious problems as a consequence of the increased displacement pressure required for circulation. Possible consequences of such a viscous sludge can be, among others, lost circulation, cement bypassing the mud leading or contamination of the cement by the mud. Contamination of the cement by mud in particular can result in unpredictable thickening time (flash set) or set properties of the cement that in the worst case may lead to a major operation failure (MOF).

[0005] As with water-based muds, some of the problems associated with the use of OBM can be addressed using a chemical wash, a fluid with a density and a viscosity close to water. Chemical washes assist mud removal by thinning, dispersing and emulsifying the mud when pumped ahead of a spacer or cement slurry. These chemical washes often include surfactants to assist in their operation. One type of surfactant that has been proposed for use in such wash fluids is an alkyl(poly)glucosides (“APG”). Examples of APGs and their use in oil well applications, particularly chemical washes can be found in U.S. Pat. No. 5,374,361; U.S. Pat. No. 5,548,197; U.S. Pat. No. 5,830,831; U.S. Pat. No. 5,977,032; U.S. Pat. No. 5,996,692; U.S. Pat. No. 6,000,412; U.S. Pat. No. 6,090,754; U.S. Pat. No. 6,110,885; U.S. Pat. No. 6,112,814; U.S. Pat. No. 6,120,199; U.S. Pat. No. 6,130,199 and EP 817,605. Certain APG compositions are disclosed in WO 99/21948; WO 96/34078 and WO 94/21655.

[0006] It is an object of the present invention to provide a surfactant composition that is suitable for well-related applications, particularly for use as a chemical wash for use with OBMs in well cementing operations.

[0007] In accordance with one aspect of the present invention, there is provided a surfactant composition comprising an alkylpolyglucoside in a solution of a mutual solvent for water and hydrocarbon.

[0008] One particular composition comprises at least one linear or branched chain C₆-C₁₀ APG. Particularly preferred APGs are C₈-C₁₀ linear and branched chained APGs, C₈ branched chain APGs, and linear C₆ APGs. These APGs can be used in isolation or in combination. The APGs can be used in a solution of a mutual solvent such as isopropyl myristate (IPM) or rapeseed methyl ester (RME) or the like. A typical ratio of surfactant(s) to mutual solvent is in the range 1:3 to 3:1.

[0009] The composition can be used to formulate a chemical wash by dissolving the composition at a concentration of about 1%-10% (e.g. 5%) by weight in water or brine. This wash can be used before placement of a cement in a well to remove OBM deposits from the wall of the well. The washes are applicable to various types of OBM, e.g. linear α olefins, low toxicity oils and esters. A wash of this type can be preceded by the use of APG and/or mutual solvent as a dilutant for drilling muds or in spacer fluids.

[0010] The present invention is considered particularly useful in providing a water-wet surface in the well or on casing so as to allow a good cement bond to form.

[0011] The present invention will now be described by way of examples, with reference to the accompanying drawings, in which:

[0012] FIGS. 1-3 show the efficacy in mud removal for three different surfactants for different types of OBM

[0013] FIGS. 4-6 show the efficacy in mud removal for two mutual solvents for different types of OBM;

[0014] FIGS. 7-18 show the effect of changing proportions of surfactant and mutual solvent on the efficacy in mud removal for different types of OBM;

[0015] FIGS. 19-21 show the effect of using different solvents with the surfactant and mutual solvents on the efficacy in mud removal different types of OBM; and

[0016] FIGS. 22-25 show the effect of changing temperature on the efficacy in mud removal.

[0017] The following method was used to test the surfactant compositions to obtain the data for FIGS. 1-25:

[0018] The cleaning efficiency of the surfactants/solvents are tested using OBMs prepared according to standardized procedures including aging by “hot rolling” at 185° F. (85° C.) during 16 hours using pressurized mud “bombs”.

[0019] A 60 mesh metallic grid is used to cover the normally smooth surface of a Chan/Fann 35 rotor and to create a rough surface to which the OBM can adhere. The rotor and metallic grid are weighed to obtain W₁. The Chan/Fann 35 is set up as normally done for an API standardized rheology measurement except that the “bob” is not used.

[0020] The rotor with the metallic grid is lowered into to the OBM so that it just covers the metallic grid part. The rotor with the metallic grid is left in the OBM under static condition for 10 minutes. When taken out, a smooth and homogenous layer of OBM covers the metallic grid. The rotor is left for 2 minutes so that any excess OBM can drip off. Finally the bottom surface is gently wiped clean. The rotor, grid and OBM are weighed upside down on a balance. The weight is noted as W₂.

[0021] The rotor with the metallic grid, now covered by a smooth OBM layer are placed in a preheated (to the desired test temperature) test cup containing the test solution (surfactant/water, solvent/water or solvent). The rotor is rotated at 100 rpm for 5 minutes and then taken out of the test solution. The rotor is left to drip for 2 minutes. The bottom is wiped to remove any drops hanging down but no OBM still adhering to the grid is removed.

[0022] The rotor is taken off the Chan/Fann 35 and weighed upside down on a balance. The weight is noted as W₃ at 5 minutes.

[0023] The rotor is now replaced in the test solution and run in an exactly same way as described above for another 5 minutes to obtain the W₃ value at 10 minutes. The process is repeated until W₃ values at 15, 20 and 30 minutes have been obtained.

[0024] The mud removal (%) is calculated using the W₁, W₂ and W₃ values.

[0025] In the test data listed below, surfactant A is a linear and branched C₈-C₁₀ APG (AG6210 obtained from Akzo-Nobel), surfactant B is a branched C₈ APG (AG6202 Akzo-Nobel),and surfactant C is a linear C₆ APG (Akzo-Nobel). The mutual solvents used are isopropyl myristate (IPM) and rapeseed methyl ester (RME) (ATOFINA). In each case the surfactant, mutual solvent, or surfactant-mutual solvent mixture is tested as a 5% by weight solution in water, sea water or 10% by weight NaCl brine according to the process described above.

[0026] Table 1 shows the various compositions tested to provide that data of FIGS. 1-3: TABLE 1 Mutual Fig. Solvent Surfactant OBM base Solution Temp. 1 A(), B(▪), Linear α Olefin Water 85° C. C(♦) 2 A(), B(▪) Low toxic mineral Water 85° C. oil 3 A(), B(▪) Ester Water 85° C.

[0027] Table 2 shows the various compositions tested to provide that data of FIGS. 4-6: TABLE 2 Fig. Mutual Solvent Surfactant OBM base Solution Temp. 4 IPM(), RME(▪) Linear α Water 85° C. Olefin 5 IPM(), RME(▪) Low toxic Water 85° C. mineral oil 6 IPM(), RME(▪) Ester Water 85° C.

[0028] Table 3 shows the various compositions tested to provide the data of FIGS. 7-12: TABLE 3 Fig. Mutual Solvent Surfactant OBM base Solution Temp. 7 () IPM (75%) A (25%) Linear α Water 85° C. (▪) IPM (50%) A (50%) Olefin (♦) IPM (75%) B (25%) (▴) IPM (25%) B (50%) 8 () IPM (75%) A (25%) Low toxic Water 85° C. (▪) IPM (50%) A (50%) mineral oil (♦) IPM (75%) B (25%) (▴) IPM (25%) B (50%) 9 () IPM (75%) A (25%) Ester Water 85° C. (▪) IPM (50%) A (50%) (♦) IPM (75%) B (25%) (▴) IPM (25%) B (50%) 10 () RME (75%) A (25%) Linear α Water 85° C. (▪) RME (50%) A (50%) Olefin (♦) RME (75%) B (25%) (▴) RME (25%) B (50%) 11 () RME (75%) A (25%) Low toxic Water 85° C. (▪) RME (50%) A (50%) mineral oil (♦) RME (75%) B (25%) (▴) RME (25%) B (50%) 12 () RME (75%) A (25%) Ester Water 85° C. (▪) RME (50%) A (50%) (♦) RME (75%) B (25%) (▴) RME (25%) B (50%)

[0029] Table 4 shows the various compositions tested to provide the data of FIGS. 13-18: TABLE 4 Fig. Mutual Solvent Surfactant OBM base Solution Temp. 13 () IPM (25%) A (56.25%), Linear α Water 85° C. B (18.75%) Olefin (▪) IPM (50%) A (37.5%), B (12.5%) (♦) IPM (75%) A (18.75%), B (6.25%) 14 () IPM (25%) A (56.25%), Low toxic Water 85° C. B (18.75%) mineral oil (▪) IPM (50%) A (37.5%), B (12.5%) (♦) IPM (75%) A (18.75%), B (6.25%) 15 () IPM (25%) A (56.25%), Ester Water 85° C. B (18.75%) (▪) IPM (50%) A (37.5%), B (12.5%) (♦) IPM (75%) A (18.75%), B (6.25%) 16 () RME (25%) A (56.25%), Linear α Water 85° C. B (18.75%) Olefin (▪) RME (50%) A (37.5%), B (12.5%) (♦) RME (75%) A (18.75%), B (6.25%) 17 () RME (25%) A (56.25%), Low toxic Water 85° C. B (18.75%) mineral oil (▪) RME (50%) A (37.5%), B (12.5%) (♦) RME (75%) A (18.75%), B (6.25%) 18 () RME (25%) A (56.25%), Ester Water 85° C. B (18.75%) (▪) RME (50%) A (37.5%), B (12.5%) (♦) RME (75%) A (18.75%), B (6.25%)

[0030] Table 5 shows the various solution bases tested to provide the data for FIGS. 19-21: TABLE 5 Mutual Fig. Solvent Surfactant OBM base Solution Temp. 19 IPM (75%) A (18.75%), Linear α () Water 85° C. B (6.25%) Olefin (▪) Sea Water (♦) 10% NaCl 20 IPM (75%) A (18.75%), Low toxic () Water 85° C. B (6.25%) mineral oil (▪) Sea Water (♦) 10% NaCl 21 IPM (75%) A (18.75%), Ester () Water 85° C. B (6.25%) (▪) Sea Water (♦) 10% NaCl

[0031] Table 6 shows the results of tests at different temperature to provide the data for FIGS. 22-25: TABLE 6 Mutual Fig. Solvent Surfactant OBM base Solution Temp. 22 IPM Ester Water () 25° C. (▪) 50° C. (♦) 85° C. 23 IPM A Ester Water () 25° C. (▪) 50° C. (♦) 85° C. 24 IPM B Ester Water () 25° C. (▪) 50° C. (♦) 85° C. 25 IPM (75%) A (18.75%) Ester Water () 25° C. B (6.25%) (▪) 50° C. (♦) 85° C. 

1. A surfactant composition comprising at least one linear or branched chain alkylpolyglucoside (APG) in a solution of a mutual solvent for water and hydrocarbon.
 2. The composition as claimed in claim 1, comprising one APG.
 3. The composition as claimed in claim 1, comprising more than one APG.
 4. The composition as claimed in any of claims 1, 2 or 3, wherein said APG comprises at least one linear or branched chain C₆-C₁₀ APG.
 5. The composition as claimed in claim 4, wherein said APG comprises a C₈-C₁₀ linear or branched chained APG, a C₈ branched chain APG, a linear C₆ APG, or combinations thereof.
 6. The composition as claimed in claim 4, wherein the mutual solvent comprises isopropyl myristate (IPM) or rapeseed methyl ester (RME).
 7. The composition as claimed in claim 4, wherein the ratio of APG to mutual solvent is in the range 1:3 to 3:1.
 8. A well treatment solution comprising at least one linear or branched chain alkylpolyglucoside (APG) in a solution of a mutual solvent for water and hydrocarbon. and water, sea water or brine.
 9. The well treatment solution as claimed in claim 8, wherein the composition is present in an amount of 1%-10% by weight.
 10. The well treatment solution as claimed in claim 9, wherein the composition is present in an amount of about 5% by weight.
 11. A method of well treatment comprising the step of circulating a well treatment solution through a well before placement of a cement slurry therein, wherein said well treatment solution comprises at least one linear or branched chain alkylpolyglucoside (APG) in a solution of a mutual solvent for water and hydrocarbon.
 12. A method of well treatment as claimed in claim 11, wherein the well has been drilled using an oil-based drilling fluid.
 13. The method of claim 11, wherein said well treatment fluid comprises one APG.
 14. The method of claim 11, wherein said well treatment fluid comprises more than one APG.
 15. The method of any of claims 11, 13, or 14, wherein said APG comprises at least one linear or branched chain C₆-C₁₀ APG.
 16. The method of claim 15, wherein said APG comprises a C₈-C₁₀ linear or branched chained APG, a C₈ branched chain APG, a linear C₆ APG, or combinations thereof.
 17. The method of claim 15, wherein the mutual solvent comprises isopropyl myristate (IPM) or rapeseed methyl ester (RME).
 18. The method of claim 15, wherein the ratio of APG to mutual solvent is in the range 1:3 to 3:1. 